A composition and method for cleaning turbine engine components (10) during servicing. An embodiment of the invention includes a colloidal mixture or slurry (22) of nanoparticles. The slurry may be nontoxic and provide optimal cleaning of tiny surface-exposed crevices (18) of braze joints and components. When a colloidal mixture is in a polar solvent, the pH of the slurry is maintained at about 5 to 9 and at the isoelectric point of the nanoparticles to minimize or prevent agglomeration. When a colloidal mixture is in a nonpolar solvent, the pH of the slurry is maintained at about 5 to 9 and at the isoelectric point of the nanoparticles to minimize or prevent agglomeration by use of surfactant additives.
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8. A method of repairing a turbine engine component, the method comprising:
applying a colloidal solution to a surface of a turbine engine component having a surface opening crevice, the colloidal solution comprising nanoparticles suspended in a solvent;
allowing the colloidal solution to penetrate the crevice and loosen a contaminant material disposed within a tip region of the crevice;
removing the colloidal solution and loosened contaminant material from the crevice and surface;
depositing a repair material onto the surface and into the crevice to penetrate the tip region of the crevice previously occupied by the contaminant material; and,
wherein the solvent comprises a non-polar solvent, and wherein the colloidal solution is characterized as:
nano silicon carbide+(either Decalin or Hexane)+polyvinyl chloride, wherein particles of the colloidal solution are characterized by: particle D(50)=50 nm, a specific surface area=130 to 35 m2/g, and 5 to 25 volatile organicsolids.
7. A method of repairing a turbine engine component, the method comprising:
applying a colloidal solution to a surface of a turbine engine component having a surface opening crevice, the colloidal solution comprising nanoparticles suspended in a solvent;
allowing the colloidal solution to penetrate the crevice and loosen a contaminant material disposed within a tip region of the crevice;
removing the colloidal solution and loosened contaminant material from the crevice and surface;
depositing a repair material onto the surface and into the crevice to penetrate the tip region of the crevice previously occupied by the contaminant material; and,
wherein the solvent comprises a non-polar solvent, and wherein the colloidal solution is characterized as:
nano silicon carbide+(either Decalin or Hexane)+polyvinyl chloride, wherein particles of the colloidal solution are characterized by: particle D(50)=20 nm, a specific surface area=130 to 35 m2/g, and 5 to 25 volatile organicsolids.
9. A method of repairing a turbine engine component, the method comprising:
applying a colloidal solution to a surface of a turbine engine component having a surface opening crevice, the colloidal solution comprising nanoparticles suspended in a solvent;
allowing the colloidal solution to penetrate the crevice and loosen a contaminant material disposed within a tip region of the crevice;
removing the colloidal solution and loosened contaminant material from the crevice and surface;
depositing a repair material onto the surface and into the crevice to penetrate the tip region of the crevice previously occupied by the contaminant material; and,
wherein the solvent comprises a non-polar solvent, and wherein the colloidal solution is characterized as:
nano silicon carbide+(either Decalin or Hexane)+polyvinyl chloride, wherein particles of the colloidal solution are characterized by: particle D(50)=80 nm, a specific surface area=130 to 35 m2/g, and 5 to 25 volatile organicsolids.
1. A method of repairing a turbine engine component, the method comprising:
applying a colloidal solution to a surface of a turbine engine component having a surface opening crevice, the colloidal solution comprising nanoparticles suspended in a solvent;
allowing the colloidal solution to penetrate the crevice and loosen a contaminant material disposed within a tip region of the crevice;
removing the colloidal solution and loosened contaminant material from the crevice and surface;
depositing a repair material onto the surface and into the crevice to penetrate the tip region of the crevice previously occupied by the contaminant material; and,
wherein the solvent comprises a non-polar solvent, and wherein the colloidal solution is characterized as:
(either nano silicon nitride or nano silicon carbide)+(either Decalin or Hexane)+polyvinyl chloride (particle D(50)), wherein particles of the colloidal solution are characterized by: particle D(50)=20 nm, 50 nm and/or 80 nma specific surface area=130 to 35 m2/g, and 5 to 25 volatile organic solids.
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The invention generally relates to turbine engine servicing, and more particularly to a composition and method of cleaning and repairing turbine engine components having surfaces containing small cracks or crevices.
Gas turbine engine components may be formed of superalloy material known for high temperature performance in terms of tensile strength, creep resistance, oxidation resistance, and corrosion resistance. The superalloy component may be a nickel-base alloy, wherein nickel is the single greatest element in the superalloy by weight. Illustrative nickel-base superalloys include at least about 40 wt % Ni, and at least one component from the group including cobalt, chromium, aluminum, tungsten, molybdenum, titanium, and iron.
Various turbine engine components crack, erode or experience conditions necessitating a repair. No joining process (braze, bond, weld, etc) will have a good result with contaminants/oxides present; e.g. brazes won't adhere, welds will have defects etc. In situations where the contaminant or oxide cannot be removed by a simple mechanical means due to its location in a crevice or crack, special cleaning techniques are required. Note that the term contaminant may be used herein to include both oxides and non-oxides, although oxide contaminants are commonly found in gas turbine applications.
Prior to servicing a turbine component, it is necessary that contaminants/oxides be removed so that a subsequent braze, for example, will adhere to the base material. A fluoride ion cleaning (FIC) procedure currently known in the industry utilizes hydrofluoric acid (HF) at elevated temperatures converting metal oxides to gaseous metal fluorides and water. Because hydrofluoric acid is an extremely corrosive acid, it is known that the acid may impede servicing by degrading an existing base material by depleting compositional elements and/or causing intergranular attack. Furthermore, hydrofluoric acid is extremely dangerous to handle and may cause skin injury or corneal damage. U.S. Pat. No. 7,303,112 describes a method of repairing a braze joint which includes the use of both an alkali metal molten salt bath and an acid solution.
Thus, there is an ongoing need for an improved turbine component repair procedure incorporating a safe and effective cleaning process.
The invention is explained in the following description in view of the drawings that show:
The present inventors have discovered that the prior art acid cleaning procedure does not always completely remove all contaminants/oxides from tiny crevices that may exist in a surface to be repaired, even after a thorough fluoride ion cleaning.
The instant invention incorporates a composition and method for cleaning surfaces such as turbine engine components and braze joints. More specifically, solutions are customized to target and remove specific oxide deposits embedded in narrow surface-opening cracks prior to a braze application. Solutions that may be considered include a colloidal mixture or slurry of nanoparticles in a solvent wherein the concentration of nanoparticles is about 0.5 wt % to about 70 wt %. Terms nanoparticle solution or colloid may be used to describe the solid-liquid mixtures, all of which contain distinct nanoparticles dispersed to various degrees in a medium. The slurry may preferably be nontoxic and provide optimal cleaning of tiny crevices existing in braze joints and other portions of gas turbine engine components. Colloid cleaners are known for the cleaning of a variety of types of surfaces, such as walls, floors, machinery, carpet, etc., and they function by breaking surface tension and holding grease, oil and dirt in suspension, thus making them easier to remove from a surface. However, the present inventors have not found them to have been used as part of a repair procedure for an in-service component, nor have they been found to have been used to specifically target the removal of contaminants/oxides from surface-opening crevices. The present inventors have recognized that the random action of the atoms of the colloidal particles will function with sufficient time to allow the cleaning solution to penetrate a surface-exposed crevice and to assist the cleaning process within the crevice by the atomic level movement of the particles against the entrapped contaminants/oxides. Furthermore, the movement of particles against the contaminants/oxides within a crevice may be enhanced by mechanical energy such as ultrasonic energy. The improved repair procedure described herein may further provide colloidal particles which are particularly effective for removing contaminants/oxides which are known to be present within the crevice.
An embodiment of the invention includes a colloidal mixture or slurry of nanoparticles in a polar solvent wherein the pH of the slurry is maintained at about 5 to 9 and at the isoelectric point of the nanoparticles to minimize or prevent flocculation (i.e., agglomeration) due to attractive van der Waals forces. Another embodiment of the invention includes a colloidal mixture or slurry of nanoparticles in a nonpolar solution where a surfactant is added to minimize or prevent agglomeration. The optional use of multiple nanoparticles with different isoelectric points within a single cleaning solution also provides a broader range of optimal cleaning. Furthermore, the properties of the particles may be selected for a particular application, such as using a relatively “soft” ceramic or one with less abrasive properties in a slurry when cleaning a softer substrate. Similarly, for areas needing more aggressive cleaning, relatively harder ceramics such as alumina and silicon carbide can be used. A hardness of a material of the nanoparticles may be selected to be harder than a hardness of the contaminant material to be removed but softer than a hardness of a material of the surface.
Another embodiment of the invention includes applying the exemplary slurries to an article or portion thereof to be cleaned, and the distance between nanoparticles in the slurry is maintained in an optimal physical excitation energy state, thereby penetrating a crevice and abrading contaminants/oxides such as iron oxide and physically removing it from a crevice.
As used herein, a nanoparticle may be any particle defined as a small object that behaves as a whole unit in terms of its transport and properties and according to size, and exhibits a range between 1 and 2500 nanometers, preferably less than 100 nm, for any dimension. There are several methods for creating nanoparticles, including both attrition and pyrolysis, which are available in various shapes including spheres, rods, and films. Suitable nanoparticles may be organic or inorganic, and include ceramics, metal oxides, carbides, nitrides, metalloids and combinations thereof. Metal oxides include crystalline solids that contain a metal cation and an oxide anion not limited to alumina, silica, anatase, zirconia, hematite, lead oxide, and magnesia. Nitrides may include any of a class of chemical compounds in which nitrogen is combined with an element of similar or lower electronegativity, such as metals, in particular boron, vanadium, silicon, titanium, and tantalum which are very refractory, resistant to chemical attack, and hard. Carbides include compounds composed of carbon and a less electronegative element and may include tungsten carbide, silicon carbide, and boron carbide.
Suitable solvents can be either polar or non polar and may include pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, dioxane, diethyl ether, dichloromethane, Tetrahydrofuran (THF), ethyl acetate, acetone, Dimethylformamide (DMF), Acetonitrile (MeCN), Dimethyl sulfoxide (DMSO), formic acid, butanol, isopopanol, propanol, ethanol, methanol, acetic acid, and water. In an embodiment where the nanoparticle solution comprises a polar solvent, the nanoparticles may be maintained at the isoelectric point. Table 1 below illustrates ceramic materials which may be used and the pH of the solution at the associated isoelectric point. The isoelectric point is the value of pH at which the colloidal particle remains stationary in an electrical field with sufficient electrostatic repulsion between particles in order to prevent agglomeration. In this embodiment, the Zeta potential of the nanoparticles may be at least +/−20 mV (i.e. greater than +20 mV or less than −20 mV) to achieve an optimal physical excitation energy state, causing nanoparticles to abrade contaminants/oxides and physically remove them from a surface or crevice.
TABLE 1
PH AT ISO ELECTRIC
CERAMIC MATERIAL
POINT (IEP)
Alumina (Al2O3)
9.1 [49]
Silicia (SiO2)
2 [50]
Anatase (Tio2)
6 [50]
Zirconia (ZrO2)
6 [50]
Hematit
7.2 [51]
Lead Oxide (PbO)
10 [52]
Magnesia (MgO)
12 [52]
Silicon Nitride (Si3N4)
8.2 [53]
Stannic Oxide (SnO2)
5.5 [9]
Zinc Oxide (ZnO)
9 [52]
Silicon Carbide (SiC)
3.5
Barium Titanate
5.5
(BaTiO3)
The pH of the solution may be adjusted before or after adding nanoparticles to form the dispersion. Suitable pH adjusters include, for example, bases such as potassium hydroxide, ammonium hydroxide, sodium carbonate, and mixtures thereof, as well as acids such as mineral acids (e.g., nitric acid and sulfuric acid) and organic acids (e.g., acetic acid, citric acid, malonic acid, succinic acid, tartaric acid, and oxalic acid). An example of solutions that may be customized to target narrow cracks for gas turbine engine applications may include the following three formulas, when in polar solvent:
nano silica+H2O+PAA/PMMA(Particle D(50)=20, 50, and 80 nm, SSA=130 to 35 m2/g, 5 to 25 v/o Solids, 1)
where PAA in this formula and throughout specification means poly acrylic acid,
where PMMA in this formula and throughout the specification means poly(methyl methacrylate),
where for Particle D(“X”) in this formula and throughout the specification, the value “X” means the size in microns that splits the distribution with half above and half below this diameter,
where SSA in this formula and throughout the specification means specific surface area,
where v/o in this formula and throughout the specification means volatile organic,
nano alumina+H2O+PAA/PMMA(Particle D(50)=20, 50, and 80 nm, SSA=130 to 35 m2/g, 5 to 25 v/o Solids) 2)
nano zirconia+H2O+PAA/PMMA(Particle D(50)=20, 50, and 80 nm, SSA=130 to 35 m2/g, 5 to 25 v/o Solids) 3)
It is an embodiment of the invention to have a variety of nanoparticles in different concentrations contained in the slurry with a pH threshold of about 5 to 9. Generally, mixed oxides will exhibit isoelectric point values intermediate to those of corresponding pure oxides. In the instance where a concentration of various nanoparticles exhibits ideal cleaning properties, but the pH is outside a desirable threshold, the pH may be adjusted and surfactants may be added to maintain the Zeta potential at least at +/−20 mV.
In an embodiment where the nanoparticle solution comprises a non polar solvent, the pH of the slurry is not critical to preventing agglomeration. In this example, however, sufficient steric repulsion can be created between particles to prevent agglomeration, which may be accomplished by the addition of the appropriate amount and type of surfactant. Surfactants include dispersants (a dispersing agent or plasticizer) and are additives that increase the plasticity or fluidity of the colloid to improve the separation of nanoparticles and prevent agglomeration and are not limited to non-surface active polymers or surface-active substances from a concentration of about 0.1% to about 30% by volume. An example of solutions that may be customized to target narrow cracks may include the following two formulas, when in non polar solvent:
nano silicon carbide+Decalin/Hexane+PVC(Particle D(50)=20, 50, and 80 nm, SSA=130 to 35 m2/g, 5 to 25 v/o Solids), 4)
where PVC in this formula and throughout the specification means polyvinyl chloride
nano silicon nitride+Decalin/Hexane+PVC(Particle D(50)=20, 50, and 80 nm, SSA=130 to 35 m2/g, 5 to 25 v/o Solids) 5)
Surfactants which may be considered can be ionic or non-ionic and include perfluorooctanoate, perfluorooctanesulfonate, sodium dodecyl sulfate, ammonium lauryl sulfate, other alkyl sulfate salts, sodium laureth sulfate, alkyl benzene sulfonate, soaps, fatty acid, cetyl trimethylammonium bromide, other alkyltrimethylammonium salts, cetylpyridinium chloride, polyethoxylated tallow amine, benzalkonium chloride, benzethonium chloride, dodecyl betaine, cocamidopropyl betaine, coco ampho glycinate, alkyl poly(ethylene oxide), alkylphenol poly(ethylene oxide), copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially called poloxamers or poloxamines), alkyl polyglucosides, octyl glucoside, decyl maltoside, fatty alcohols, cetyl alcohol, oleyl alcohol, cocamide monoethanolamine (MEA), cocamide diethanolamine (DEA), and polysorbates.
It is one embodiment of the present invention to apply a slurry to a braze which forms a portion of a surface of a gas turbine engine exposed to a working fluid during a post-operation service activity. The slurry may be a mixture of different nanoparticles in suspension. For example, combining a nitride and carbide at different concentrations, and maintaining the mixture at its isoelectric point in a solution of water, for example. The composition may be applied to the braze by known methods in the art, not limited to spray, brush, or bath applications.
It is a further embodiment of the invention to provide additional cleaning to a region in order to complement the action of the colloid with an appropriate mechanical action, such as by applying ultrasonic energy. A method of cleaning may include the steps of: applying a colloidal solution to a surface; agitating the colloidal solution to mechanically engage the nanoparticles against a contaminant material disposed within the crevices to loosen the contaminant material from the crevices; and removing the colloidal solution and loosened contaminant material from the surface. A vacuum may be used to remove loosened contaminants/oxides from the surface and from within crevices. Upon cleaning of a surface and its surface-exposed crevices using a colloidal solution as described above, a subsequent material overlay (braze, weld, transient liquid phase bonding, etc.) will bond optimally with the cleaned surface and will better fill the cleaned crevice regions than can be achieved with prior art cleaning procedures. The improved sealing of crevice tips achieved with the present invention will reduce or prevent premature cracking at the crevice site that has been experienced with prior art cleaning/repair procedures.
While various embodiments of the present invention have been shown and described herein, it will be obvious that such embodiments are provided by way of example only. Numerous variations, changes and substitutions may be made without departing from the invention herein. Accordingly, it is intended that the invention be limited only by the spirit and scope of the appended claims.
Kulkarni, Anand A., Abdo, Zafir A. M., Caso, Jr., Diego L., Manjooran, Navin J., Hunt, Anita Marie
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